WO2019151774A1 - Matériau actif d'anode, procédé de préparation de matériau actif d'anode, anode comprenant un matériau actif d'anode et batterie secondaire comprenant l'anode - Google Patents

Matériau actif d'anode, procédé de préparation de matériau actif d'anode, anode comprenant un matériau actif d'anode et batterie secondaire comprenant l'anode Download PDF

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WO2019151774A1
WO2019151774A1 PCT/KR2019/001297 KR2019001297W WO2019151774A1 WO 2019151774 A1 WO2019151774 A1 WO 2019151774A1 KR 2019001297 W KR2019001297 W KR 2019001297W WO 2019151774 A1 WO2019151774 A1 WO 2019151774A1
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active material
negative electrode
electrode active
lithium
sio
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PCT/KR2019/001297
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English (en)
Korean (ko)
Inventor
이수민
이용주
조래환
김동혁
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주식회사 엘지화학
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Priority to CN201980006352.9A priority Critical patent/CN111466045B/zh
Priority to US16/772,585 priority patent/US11605811B2/en
Priority to EP19746961.2A priority patent/EP3709405A4/fr
Publication of WO2019151774A1 publication Critical patent/WO2019151774A1/fr
Priority to US18/107,263 priority patent/US20230197938A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/24—Alkaline-earth metal silicates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/32—Alkali metal silicates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a negative electrode active material, a method of manufacturing the negative electrode active material, a negative electrode including the negative electrode active material, and a secondary battery including the negative electrode.
  • the negative electrode active material is SiO x (0 ⁇ x ⁇ 2) and lithium A core comprising a containing compound; And a shell disposed on the core, the shell including SiO x (0 ⁇ x ⁇ 2) and magnesium silicate.
  • a representative example of an electrochemical device using such electrochemical energy is a secondary battery, and its use area is gradually increasing.
  • portable devices such as portable computers, portable telephones, cameras, and the like
  • secondary batteries high energy density, that is, high capacity lithium secondary batteries
  • a secondary battery is composed of a positive electrode, a negative electrode, an electrolyte, and a separator.
  • the negative electrode includes a negative electrode active material for inserting and detaching lithium ions from the positive electrode, and silicon-based particles having a large discharge capacity may be used as the negative electrode active material.
  • silicon-based particles such as SiO x (0 ⁇ x ⁇ 2) have low initial efficiency and excessively change in volume during charge and discharge. Therefore, a problem occurs that the life of the battery is reduced. In particular, as the charge and discharge cycles are repeated, cracks are generated in the silicon-based particles, resulting in deterioration of life and deterioration of mechanical stability.
  • Patent Document 1 Republic of Korea Patent Publication No. 10-2015-0112746
  • One problem to be solved by the present invention is a negative electrode active material and a method of manufacturing the same, including the negative electrode active material which has a high initial efficiency and can effectively control the volume change during the charging and discharging process of the secondary battery to improve the life characteristics of the battery It is to provide a negative electrode and a secondary battery.
  • a core including SiO x (0 ⁇ x ⁇ 2) and a lithium-containing compound; And a shell disposed on the core, the shell including SiO x (0 ⁇ x ⁇ 2) and magnesium silicate.
  • the step of mixing the SiO x (0 ⁇ x ⁇ 2) particles and magnesium powder to form a first mixture First heat treating the first mixture to form silicon-based particles comprising magnesium silicate; Mixing the silicon-based particles and lithium powder to form a second mixture; And a second heat treatment of the second mixture.
  • a negative electrode including the negative electrode active material is provided.
  • a secondary battery including the negative electrode is provided.
  • the negative electrode active material includes a core including a lithium-containing compound and a shell including magnesium silicate.
  • a process of forming a magnesium silicate and a process of forming a lithium-containing compound relative to the core portion where the magnesium silicate is not formed are relatively performed, so that the metal-containing compound may be uniformly distributed in the negative electrode active material. . Accordingly, nonuniform volume expansion of the negative electrode active material may be suppressed when the battery is driven, thereby reducing cracks.
  • magnesium silicate such as magnesium silicate, has a high hardness, the volume expansion and crack generation of the negative electrode active material may be further suppressed by the shell including the magnesium silicate. Accordingly, the initial efficiency of the secondary battery can be improved, and the volume expansion of Si and / or SiO 2 included in the negative electrode active material can be effectively controlled to improve the life characteristics of the battery.
  • the terms “comprise”, “comprise” or “have” are intended to indicate that there is a feature, number, step, component, or combination thereof, that is, one or more other features, It should be understood that it does not exclude in advance the possibility of the presence or addition of numbers, steps, components, or combinations thereof.
  • a negative active material according to an embodiment of the present invention is a core containing SiO x (0 ⁇ x ⁇ 2) and a lithium-containing compound; And a shell disposed on the core, the shell including SiO x (0 ⁇ x ⁇ 2) and magnesium silicate.
  • the core may comprise SiO x (0 ⁇ x ⁇ 2).
  • the SiO x (0 ⁇ x ⁇ 2) may be in a form containing Si and SiO 2 . That is, x corresponds to the number ratio of O to Si contained in the SiO x (0 ⁇ x ⁇ 2).
  • X may be more specifically 0.5 to 1.5.
  • the SiO 2 may be crystalline SiO 2 .
  • the crystalline SiO 2 may be quartz, cristobalite or tridymite.
  • the average particle diameter (D 50 ) of the core may be 1 ⁇ m to 20 ⁇ m, and specifically 3 ⁇ m to 10 ⁇ m.
  • the average particle diameter (D 50 ) may be defined as a particle diameter based on 50% of the particle size distribution of the particles.
  • the average particle diameter D 50 may be measured using, for example, a laser diffraction method. In general, the laser diffraction method can measure the particle diameter of several mm from the submicron region, and high reproducibility and high resolution can be obtained.
  • the core may comprise a lithium containing compound.
  • the lithium-containing compound may be a compound formed by doping lithium metal into silicon-based particles during the preparation of the negative electrode active material.
  • the lithium-containing compound may improve the initial efficiency of the secondary battery and increase the energy density of the negative electrode.
  • the metal silicate and the metal-containing compound including the lithium-containing compound may be uniformly present in the negative electrode active material, so that uneven volume expansion may be suppressed during battery charging and discharging, resulting in crack generation. This can be reduced. Accordingly, the life characteristics of the battery can be improved.
  • the lithium-containing compound may include at least one of lithium silicate and lithium silicide.
  • the lithium silicate may include at least one selected from the group consisting of Li 2 Si 2 O 5 , Li 2 SiO 3, and Li 4 SiO 4 . Since the core includes lithium silicate, the initial efficiency of the secondary battery and the energy density of the negative electrode may be improved.
  • the lithium silicide may include Li y Si (2 ⁇ y ⁇ 5), and specifically, may include at least one selected from the group consisting of Li 4.4 Si, Li 3.75 Si, Li 3.25 Si, and Li 2.33 Si. have.
  • the lithium silicate included in the core may be included in an amount of 0.1% to 50% by weight, specifically, 1% to 30% by weight, and more specifically 3% to 3% by weight, based on the total weight of the negative electrode active material. It may be included in 10% by weight. When the above range is satisfied, the initial efficiency and lifespan characteristics of the battery may be improved.
  • the lithium silicate type may be measured by XRD, and the content of the lithium silicate may be measured by an ICP method, but is not necessarily limited thereto.
  • the shell may be disposed on the core. Specifically, the shell may cover at least a portion of the core surface, and more specifically, cover all of the core surface.
  • the shell may comprise SiO x (0 ⁇ x ⁇ 2). At this time, since SiO x (0 ⁇ x ⁇ 2) is the same as that of SiO x (0 ⁇ x ⁇ 2), the description is omitted.
  • the shell may comprise magnesium silicate.
  • the magnesium silicate may be a compound formed by doping magnesium metal particles with silicon-based particles during the preparation of the negative electrode active material.
  • the magnesium silicate may improve the initial efficiency of the secondary battery.
  • magnesium silicate such as magnesium silicate, has a high hardness, the volume expansion and crack generation of the negative electrode active material may be further suppressed by the shell including the magnesium silicate.
  • the magnesium silicate may include at least one of Mg 2 SiO 4 and MgSiO 3 . Since the shell includes the magnesium silicate, volume expansion and cracking of the negative electrode active material may be further suppressed.
  • the magnesium silicate included in the shell may be included in an amount of 0.1 wt% to 50 wt%, specifically 1 wt% to 30 wt%, and more specifically 3 wt% to It may be included in 10% by weight. When the above range is satisfied, the initial efficiency and lifespan characteristics of the battery may be improved.
  • the magnesium silicate type may be measured by XRD, and the magnesium silicate content may be measured by an ICP method, but is not necessarily limited thereto.
  • the shell may have a thickness of 0.02 ⁇ m to 5 ⁇ m, specifically 0.3 ⁇ m to 3 ⁇ m, and more specifically 0.5 ⁇ m to 1 ⁇ m. When the above range is satisfied, the initial efficiency and lifespan characteristics of the battery may be further improved. Although not limited thereto, the thickness of the shell may be measured by SEM. In addition, the thickness of the shell from the surface of the negative electrode active material means the distance from the point where the magnesium silicate is detected.
  • the shell may further comprise a lithium containing compound, where the lithium containing compound may be the same as the lithium containing compound contained in the core. Therefore, the lithium-containing compound included in the core may be included in an amount of 70% by weight to 100% by weight based on the total weight of the lithium-containing compound present in the negative electrode active material, specifically, 90% by weight to 100% by weight. In other words, when the lithium-containing compound included in the core is 100% by weight based on the total weight of the lithium-containing compound present in the negative electrode active material, the lithium-containing compound is present only in the core. On the contrary, when it is not 100% by weight, it means that the lithium-containing compound may also be present in the shell.
  • the average particle diameter (D 50 ) of the negative electrode active material may be 1 ⁇ m to 20 ⁇ m, and specifically 3 ⁇ m to 10 ⁇ m.
  • the side reaction with the electrolyte may be reduced, and the defective rate may be reduced in the process of coating and rolling the negative electrode slurry on the current collector.
  • crack generation of the negative electrode active material may be reduced during charging / discharging of the battery.
  • the heat treatment proceeds at a relatively low temperature, not using a manufacturing method accompanied by high temperature heat treatment such as milling, so that the negative electrode active material does not include silicon grains or even contains silicon crystal grains. May have a small particle size. Accordingly, when the battery is charged and discharged, excessive volume expansion of the negative electrode active material can be suppressed, so that the life characteristics of the battery can be improved.
  • the grain size of the silicon grains may be 50 nm or less, specifically 30 nm or less, more specifically 20 nm or less, for example, 8 nm to 15 nm.
  • Presence and particle size of the silicon crystal grains can be confirmed by XRD (X-Ray Diffraction) analysis method. Specifically, after checking the (111) peak of the silicon by XRD analysis of the prepared negative active material, the particle size (L) of the silicon crystal grains can be calculated through the P.Sherrer equation.
  • L is the particle size of the silicon grains (unit: nm)
  • ⁇ is the shape factor 0.9 (elements for particle shape, no unit)
  • ⁇ is 0.154056 (unit: nm)
  • ⁇ is the (111) peak half-width ( Unit: radian).
  • the negative electrode active material according to another embodiment of the present invention is similar to the negative electrode active material according to the above-described embodiment, except that it further includes a carbon coating layer disposed on the shell. Thus, the difference will be described.
  • the carbon coating layer may be disposed on the shell. Specifically, the carbon coating layer may cover at least a portion of the shell surface, more specifically, the carbon coating layer may cover 50% to 100% of the surface of the shell portion. Since the conductivity of the negative electrode active material may be improved by the carbon coating layer, initial efficiency, lifespan characteristics, and battery capacity characteristics of the secondary battery may be improved.
  • the carbon coating layer may be 1% by weight to 15% by weight based on the total weight of the negative electrode active material, and specifically 3% by weight to 10% by weight. When satisfying the above range, the life characteristics and output characteristics of the battery can be further improved.
  • the carbon coating layer may include a carbon-based material.
  • the carbonaceous material may include at least one of amorphous carbon and crystalline carbon.
  • the crystalline carbon may further improve the conductivity of the negative electrode active material.
  • the crystalline carbon may include at least one selected from the group consisting of florene, carbon nanotubes, and graphene.
  • the amorphous carbon can appropriately maintain the strength of the carbon coating layer, to suppress expansion of the core.
  • the amorphous carbon may be a carbon-based material formed by using at least one carbide or hydrocarbon selected from the group consisting of tar, pitch and other organic materials as a source of chemical vapor deposition.
  • the carbide of the other organic material may be a carbide of an organic material selected from carbides of sucrose, glucose, galactose, fructose, lactose, manos, ribose, aldohexose or kedohexose, and combinations thereof.
  • the hydrocarbon may be a substituted or unsubstituted aliphatic or alicyclic hydrocarbon, a substituted or unsubstituted aromatic hydrocarbon.
  • the aliphatic or alicyclic hydrocarbons of the substituted or unsubstituted aliphatic or alicyclic hydrocarbons may be meterin, ether, ethylene, acetylene, propane, butane, butene, pentane, isobutane or hexane.
  • the aromatic hydrocarbons of the substituted or unsubstituted aromatic hydrocarbons include benzene, toluene, xylene, styrene, ethylbenzene, diphenylmethane, naphthalene, phenol, cresol, nitrobenzene, chlorobenzene, indene, coumarone, pyridine, Anthracene, phenanthrene, and the like.
  • the carbon coating layer may have a thickness of 10 nm to 1000 nm, specifically 100 nm to 800 nm, and more specifically 200 nm to 500 nm. When satisfying the above range, the life characteristics and output characteristics of the battery can be further improved. Although not limited thereto, the thickness of the carbon coating layer may be measured by SEM or TEM.
  • a method of manufacturing a negative active material includes: mixing a SiO x (0 ⁇ x ⁇ 2) particle and a magnesium powder to form a first mixture; First heat treating the first mixture to form silicon-based particles comprising magnesium silicate; Mixing the silicon-based particles and lithium powder to form a second mixture; And a second heat treatment of the second mixture.
  • the magnesium silicate is the same as the magnesium silicate mentioned in the above embodiments, and thus description thereof is omitted.
  • the weight ratio of the SiO x (0 ⁇ x ⁇ 2) particles and the magnesium powder may be 99: 1 to 70:30, specifically 95: 5 to 80:20 days And more specifically 93: 7 to 84:16.
  • an appropriate amount of magnesium silicate is formed, so that the initial efficiency and lifespan characteristics of the battery can be further improved.
  • the average particle diameter (D 50 ) of the SiO x (0 ⁇ x ⁇ 2) particles may be 1 ⁇ m to 20 ⁇ m, specifically 3 ⁇ m to 10 ⁇ m.
  • the first heat treatment may be performed at 300 °C to 1200 °C, specifically may be carried out at 500 °C to 1100 °C, more specifically 800 °C to 1000 °C Can be proceeded from. Proceeding to the above temperature, an appropriate amount of magnesium silicate can be formed while preventing the growth of silicon crystals in the negative electrode active material, so that the battery life performance can be improved.
  • the weight ratio of the silicon-based particles and the lithium powder may be 99: 1 to 70:30, specifically 98: 2 to 80:20, and more specifically 97: 3 to 90:10.
  • an appropriate amount of lithium-containing compound can be formed, so that the initial efficiency and lifespan characteristics of the battery can be further improved.
  • the second heat treatment may be performed at 100 ° C to 1000 ° C, specifically, may proceed at 300 ° C to 900 ° C, more specifically at 400 ° C to 800 ° C Can be. Proceeding to the above temperature, it is possible to form an appropriate amount of the lithium-containing compound while preventing the growth of the silicon crystals in the negative electrode active material, the battery life performance can be improved.
  • a lithium-containing compound may be formed at the center of the silicon-based particle (corresponding to the core described in an embodiment). Specifically, after magnesium silicate is formed near the surface of the silicon-based particles by the first heat treatment, there is almost no SiO 2 in which the lithium metal reacts with the silicon-based particles in the region where the magnesium silicate is formed even after the second heat treatment. Do not. Accordingly, most of the lithium-containing compound may be formed at the center of the silicon-based particles in which SiO 2 to react is present.
  • the method of manufacturing the negative electrode active material according to another embodiment of the present invention is similar to the method of manufacturing the negative electrode active material of the other embodiments described above, but differs in that it further comprises the step of forming a carbon coating layer. Thus, the difference will be described.
  • the method may further include forming a carbon coating layer on the second heat-treated silicon-based particle surface.
  • the carbon coating layer is the same as the carbon coating layer described in the above-described negative active material of another embodiment.
  • the carbon coating layer may be formed by arranging a carbon precursor on the silicon-based particles and then heat-treating them, but is not necessarily limited thereto.
  • the negative electrode according to another embodiment of the present invention may include a negative electrode active material, wherein the negative electrode active material is the same as the negative electrode active material of the above-described embodiments.
  • the negative electrode may include a current collector and a negative electrode active material layer disposed on the current collector.
  • the negative electrode active material layer may include the negative electrode active material.
  • the negative electrode active material layer may further include a binder and / or a conductive material.
  • the current collector may be any conductive material without causing chemical change in the battery, and is not particularly limited.
  • the current collector may be copper, stainless steel, aluminum, nickel, titanium, calcined carbon, or a surface treated with carbon, nickel, titanium, silver, or the like on the surface of aluminum or stainless steel.
  • a transition metal that adsorbs carbon such as copper and nickel can be used as the current collector.
  • the thickness of the current collector may be 6 ⁇ m to 20 ⁇ m, but the thickness of the current collector is not limited thereto.
  • the binder is polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidene fluoride (polyvinylidenefluoride), polyacrylonitrile, polymethylmethacrylate, polymethylmethacrylate, poly Vinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, ethylene-propylene-diene monomer (EPDM), liquor It may include at least one selected from the group consisting of fonned EPDM, styrene butadiene rubber (SBR), fluorine rubber, poly acrylic acid, and a substance in which hydrogen thereof is replaced with Li, Na, or Ca. It may also include various copolymers thereof.
  • PVDF-co-HFP polyvinylidene fluoride-hexafluoro
  • the conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • Examples of the conductive material include graphite such as natural graphite and artificial graphite; Carbon blacks such as carbon black, acetylene black, Ketjen black, channel black, farnes black, lamp black and thermal black; Conductive fibers such as carbon fibers and metal fibers; Conductive tubes such as carbon nanotubes; Metal powders such as fluorocarbon, aluminum and nickel powders; Conductive whiskers such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • a secondary battery according to another embodiment of the present invention may include a negative electrode, a positive electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte, and the negative electrode is the same as the negative electrode described above. Since the cathode has been described above, a detailed description thereof will be omitted.
  • the positive electrode may be formed on the positive electrode current collector and the positive electrode current collector, and may include a positive electrode active material layer including the positive electrode active material.
  • the positive electrode current collector is not particularly limited as long as it is conductive without causing chemical change in the battery.
  • the positive electrode current collector is made of stainless steel, aluminum, nickel, titanium, calcined carbon, or carbon on the surface of aluminum or stainless steel. Surface treated with nickel, titanium, silver, or the like may be used.
  • the positive electrode current collector may have a thickness of about 3 to 500 ⁇ m, and may form fine irregularities on the surface of the current collector to increase adhesion of the positive electrode active material.
  • it can be used in various forms, such as a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven body.
  • the cathode active material may be a cathode active material that is commonly used.
  • the cathode active material may be a layered compound such as lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 ), or a compound substituted with one or more transition metals; Lithium iron oxides such as LiFe 3 O 4 ; Lithium manganese oxides such as Li 1 + c1 Mn 2-c1 O 4 (0 ⁇ c1 ⁇ 0.33), LiMnO 3 , LiMn 2 O 3 , LiMnO 2 ; Lithium copper oxide (Li 2 CuO 2 ); Vanadium oxides such as LiV 3 O 8 , V 2 O 5 , Cu 2 V 2 O 7, and the like; Represented by the formula LiNi 1-c2 M c2 O 2 , wherein M is at least one selected from the group consisting of Co, Mn, Al, Cu, Fe, Mg, B, and Ga, and satis
  • the cathode active material layer may include a cathode conductive material and a cathode binder together with the cathode active material described above.
  • the cathode conductive material is used to impart conductivity to the electrode, and in the battery constituted, the cathode conductive material may be used without particular limitation as long as it has electron conductivity without causing chemical change.
  • Specific examples thereof include graphite such as natural graphite and artificial graphite; Carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, summer black and carbon fiber; Metal powder or metal fibers such as copper, nickel, aluminum, and silver; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Or conductive polymers such as polyphenylene derivatives, and the like, or a mixture of two or more kinds thereof may be used.
  • the positive electrode binder serves to improve adhesion between the positive electrode active material particles and the positive electrode active material and the positive electrode current collector.
  • specific examples include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethyl cellulose (CMC).
  • the separator separates the negative electrode from the positive electrode and provides a passage for lithium ions, and can be used without particular limitation as long as the separator is used as a separator in a secondary battery. In particular, it has a low resistance to ion migration of the electrolyte and an excellent ability to hydrate the electrolyte. It is preferable.
  • a porous polymer film for example, a porous polymer film made of a polyolefin-based polymer such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / methacrylate copolymer or the like Laminate structures of two or more layers may be used.
  • porous nonwoven fabrics such as nonwoven fabrics made of high melting point glass fibers, polyethylene terephthalate fibers and the like may be used.
  • a coated separator including a ceramic component or a polymer material may be used to secure heat resistance or mechanical strength, and may be optionally used as a single layer or a multilayer structure.
  • the electrolyte may include an organic liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel polymer electrolyte, a solid inorganic electrolyte, a molten inorganic electrolyte, and the like, which can be used in manufacturing a lithium secondary battery, but are not limited thereto.
  • the electrolyte may include a non-aqueous organic solvent and a metal salt.
  • non-aqueous organic solvent for example, N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butylo lactone, 1,2-dime Methoxy ethane, tetrahydroxy franc, 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolon, formamide, dimethylformamide, dioxoron, acetonitrile, nitromethane, methyl formate, Methyl acetate, phosphate triester, trimethoxy methane, dioxorone derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, ethers, pyrion
  • An aprotic organic solvent such as methyl acid or ethyl
  • ethylene carbonate and propylene carbonate which are cyclic carbonates among the carbonate-based organic solvents, may be preferably used as high-viscosity organic solvents because they have high dielectric constants to dissociate lithium salts well, such as dimethyl carbonate and diethyl carbonate.
  • high-viscosity organic solvents because they have high dielectric constants to dissociate lithium salts well, such as dimethyl carbonate and diethyl carbonate.
  • an electrolyte having a high electrical conductivity can be made, and thus it can be more preferably used.
  • the metal salt may be a lithium salt
  • the lithium salt is a material that is readily soluble in the non-aqueous electrolyte, for example, is in the lithium salt anion F -, Cl -, I - , NO 3 -, N (CN ) 2 -, BF 4 -, ClO 4 -, PF 6 -, (CF 3) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF - , (CF 3) 6 P - , CF 3 SO 3 -, CF 3 CF 2 SO 3 -, (CF 3 SO 2) 2 N -, (FSO 2) 2 N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2 ) 2 CH -, (SF 5) 3 C -, (CF 3 SO 2) 3 C -, CF 3 (CF 2) 7 SO 3 -, CF 3 CO 2 -, CH 3 CO 2 -
  • the electrolyte includes, for example, haloalkylene carbonate-based compounds such as difluoro ethylene carbonate, pyridine, tri, etc. for the purpose of improving battery life characteristics, reducing battery capacity, and improving discharge capacity of the battery.
  • haloalkylene carbonate-based compounds such as difluoro ethylene carbonate, pyridine, tri, etc.
  • Ethyl phosphite triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazolidinone, N, N-substituted imida
  • One or more additives such as zolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxy ethanol or aluminum trichloride may be included.
  • a battery module including the secondary battery as a unit cell and a battery pack including the same are provided. Since the battery module and the battery pack include the secondary battery having high capacity, high rate characteristics, and cycle characteristics, a medium-large device selected from the group consisting of an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, and a power storage system It can be used as a power source.
  • mixed negative active material and graphite prepared by mixing the negative electrode active material and graphite in a weight ratio of 1: 9, conductive material carbon black, binder carboxymethyl cellulose (CMC) and styrene butadiene rubber (SBR) 5 g of a mixture was prepared by mixing at a weight ratio of 1: 1.7: 1.5. 28.9 distilled water was added to the mixture to prepare a negative electrode slurry.
  • the negative electrode slurry was applied and dried on a copper (Cu) metal thin film, which is a negative electrode current collector having a thickness of 20 ⁇ m. At this time, the temperature of the air circulated was 60 °C. Subsequently, a roll was pressed and dried in a vacuum oven at 130 ° C. for 12 hours, and then spun into a circle of 1.4875 cm 2 to prepare a negative electrode.
  • Cu copper
  • the prepared negative electrode was a lithium (Li) metal thin film cut in a circular shape of 1.7671 cm 2 as a positive electrode.
  • EMC methyl ethyl carbonate
  • EC ethylene carbonate
  • a negative electrode active material was prepared in the same manner as in Example 1, except that 35 g of magnesium powder was used. As a result of analyzing the prepared negative active material by XRD, ICP and SEM, a core containing lithium silicate and a shell containing magnesium silicate were observed.
  • a negative electrode and a secondary battery were prepared in the same manner as in Example 1.
  • a negative electrode active material was manufactured in the same manner as in Example 1, except that 0.5 g of magnesium powder was used. As a result of analyzing the prepared negative active material by XRD, ICP and SEM, a core containing lithium silicate and a shell containing magnesium silicate were observed.
  • a negative electrode and a secondary battery were prepared in the same manner as in Example 1.
  • a negative electrode and a secondary battery were prepared in the same manner as in Example 1.
  • a mixture was formed by mixing 100 g of SiO having an average particle diameter (D 50 ) of 6 ⁇ m and 6 g of lithium powder having an average particle diameter (D 50 ) of 5 ⁇ m. Thereafter, the mixture was introduced into a chamber, and heat was performed by applying heat at 750 ° C. for 2 hours. Through this, a negative electrode active material was prepared.
  • lithium silicate generally exists in the negative electrode active material. That is, lithium silicate was dispersed and present in the negative electrode active material such that the core and the shell could not be distinguished with or without lithium silicate.
  • a negative electrode and a secondary battery were prepared in the same manner as in Example 1.
  • each of the lithium silicate and magnesium silicate were all based on the total weight of the negative electrode active material, and were measured by the method of ICP.
  • the size of the core and the thickness of the shell were measured by SEM.
  • the particle size of the silicon crystal grains in the anode active material was derived by applying the P.Sherrer equation to the (111) peak of silicon derived through X-ray diffraction (XRD) analysis.
  • Test Example 1 Evaluation of discharge capacity, initial efficiency, lifetime characteristics, and crack occurrence
  • Discharge capacity (mAh / g) and initial efficiency (%) were derived through the result at the time of single charge / discharge. Specifically, the initial efficiency (%) was derived by the following calculation.
  • Capacity retention rate (%) (49 discharge capacity / 1 discharge capacity) ⁇ 100
  • crack generation was determined by measuring the cross section of the negative electrode active material in the negative electrode after completion of the capacity retention measurement.
  • Example 2 and 3 since the discharge capacity and capacity retention rate of Examples 2 and 3 are smaller than those of Example 1, the discharge capacity and capacity retention rate can be further improved when the content of magnesium silicate included in the shell satisfies an appropriate level. It was confirmed that there is.
  • the metal-containing compound in the negative electrode active material since too much or too little magnesium silicate is included in the negative electrode active material, the metal-containing compound in the negative electrode active material is distributed relatively non-uniformly compared to Example 1, so that the volume expansion of the negative electrode active material is suppressed. Appears to be at a lower level than Example 1.
  • Example 3 since the shell contains less magnesium silicate and the hardness of the shell is lower than that of Examples 1 and 2, the capacity retention rate is inferior to Examples 1 and 2.

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Abstract

La présente invention concerne un matériau actif d'anode comprenant : un noyau comprenant du SiOx(0 ≤ x < 2) et un composé contenant du lithium ; et une enveloppe disposée sur le noyau et comprenant du SiOx(0 ≤ x < 2) et du silicate de magnésium.
PCT/KR2019/001297 2018-01-30 2019-01-30 Matériau actif d'anode, procédé de préparation de matériau actif d'anode, anode comprenant un matériau actif d'anode et batterie secondaire comprenant l'anode WO2019151774A1 (fr)

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CN201980006352.9A CN111466045B (zh) 2018-01-30 2019-01-30 负极活性材料、其制备方法、包含所述负极活性材料的负极和包含所述负极的二次电池
US16/772,585 US11605811B2 (en) 2018-01-30 2019-01-30 Negative electrode active material, preparation method thereof, negative electrode including the negative electrode active material, and secondary battery including the negative electrode
EP19746961.2A EP3709405A4 (fr) 2018-01-30 2019-01-30 Matériau actif d'anode, procédé de préparation de matériau actif d'anode, anode comprenant un matériau actif d'anode et batterie secondaire comprenant l'anode
US18/107,263 US20230197938A1 (en) 2018-01-30 2023-02-08 Negative electrode active material, preparation method thereof, negative electrode including the negative electrode active material, and secondary battery including the negative electrode

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